Asymmetrical 1:2 cobalt complexes of certain substituted phenylazonaphthalenes

ABSTRACT

Disclosed are homogeneous complexes of the formula   &lt;IMAGE&gt; wherein R1 is hydrogen, alkyl, phenyl or substituted phenyl, &lt;IMAGE&gt;  WHEREIN ONE Q is hydrogen and the other is sulfo, and N IS 0 OR 1 (THE SULFO GROUP BEING IN THE 5- OR 6-POSITION WHEN N IS 1), R4 is hydrogen, alkyl, alkoxy, chloro, bromo or nitro, R5 is hydrogen, alkyl, alkoxy, chloro, bromo, nitro or sulfo, WITH THE PROVISO THAT WHEN ONE OF R4 and R5 is hydrogen, the other is other than hydrogen and is in the 4- or 5-position and when both are other than hydrogen, one is in the 4-position and the other is in the 5- or 6-position, ONE OF R6 and R7 is hydrogen, chloro or nitro and the other is hydrogen, sulfamoyl or substituted sulfamoyl, and XDis  &lt;IMAGE&gt; &lt;IMAGE&gt;  &lt;IMAGE&gt;   wherein one of R10 and R11 is hydrogen and the other is hydrogen, chloro, alkyl, alkoxy or trifluoromethyl, R12 is hydrogen or methyl, R13 is methyl, chloro or bromo, with the proviso that R12 is hydrogen when R13 is chloro or bromo, Y1 is hydrogen or acylamino, Y2 is hydrogen, alkyl, alkoxy, chloro or bromo, Y+HD 3 is hydrogen or 5- or 6-sulfamoyl, alkylsulfamoyl or hydroxyalkylsulfamoyl, and M(+) is hydrogen or a non-chromophoric cation, wherein the asterisks indicate the carbon atom attached to the azo group, with the proviso that the complex contains a single sulfamoyl or substituted sulfamoyl group and a single sulfo group which is in salt form, and mixtures of such complexes. The complexes and mixtures are useful for dyeing and printing nitrogen-containing organic substrates, for example, polyamides such as wool, silk and nylon, polyurethanes and leather.

The present invention relates to homogeneous asymmetric 1:2 cobalt complexes and mixtures of such complexes.

More particularly, the invention provides homogenous asymmetric 1:2 cobalt complexes of formula I, ##STR4## in which R₁ is hydrogen, (C₁₋₄) alkyl or a group of the formula ##STR5## in which R₂ is hydrogen, chlorine, bromine, methyl, methoxy or trifluoromethyl, and

R₃ is hydrogen, methyl, methoxy or --SO₃ H,

B is a group of the formula ##STR6## wherein one of Q and Q' is SO₃ H and the other is hydrogen, and m is 1 or 2 and when m is 2 the sulpho group is in the 5- or 6-position,

R₄ is hydrogen, (C₁₋₄)alkyl, (C₁₋₄)alkoxy, chlorine, bromine or nitro,

R₅ has one of the significances of R₄ or is --SO₃ H, with the proviso that when one of R₄ and R₅ is hydrogen and the other is other than hydrogen, the substituent is in the 4- or 5-position and where both R₄ and R₅ are other than hydrogen the substituents are in the 4,5- or 4,6-positions,

one of R₆ and R₇ is hydrogen, chloro or nitro and the other is hydrogen or --SO₂ NR₈ R₉,

either R₈ is hydrogen or unsubstituted or substituted (C₁₋₄)alkyl,

R₉ is hydrogen or unsubstituted or substituted (C₁₋₄)alkyl, (C₅₋₇)cycloalkyl or phenyl,

or R₈ and R₉, together with the nitrogen atom to which they are bound, form a non-aromatic 5- or 6-membered heterocyclic ring which contains no further or a further hetero atom,

--X--D-- is a divalent radical of formula (c), (d), (e), (f), (g) or (h), ##STR7## wherein one of R₁₀ and R₁₁ is hydrogen, chlorine, (C₁₋₂)alkyl, (C₁₋₂)alkoxy or trifluoromethyl and the other is hydrogen,

R₁₂ is hydrogen or methyl,

R₁₃ is methyl, chlorine or bromine, with the proviso that when R₁₃ is chlorine or bromine, R₁₂ is hydrogen,

Y₁ is hydrogen, --NHCOR₁₄, --NHCOOR₁₅ or --NHSO₂ Z,

R₁₄ and R₁₅ are unsubstituted or substituted (C₁₋₄)alkyl or phenyl,

Z is (C₁₋₄)alkyl, unsubstituted or substituted phenyl or --NR₁₆ R₁₇,

R₁₆ is hydrogen, methyl or ethyl,

R₁₇ is methyl or ethyl,

Y₂ is hydrogen, (C₁₋₂)alkyl, (C₁₋₂)alkoxy, chlorine or bromine,

Y₃ is hydrogen or --SO₂ NHR₁₈, any such --SO₂ NHR₁₈ group being in the 5- or 6-position,

R₁₈ is hydrogen, (C₁₋₄)alkyl or (C₂₋₄)hydroxyalkyl,

M.sup.⊕ is hydrogen or a non-chromophoric cation, and

the asterisks indicate the carbon atom attached to the azo group,

with the provisos that the molecule contains a single sulpho group and a single sulphonamide group, which sulpho group is in salt form, and that the molecule is free from ##STR8## and mixtures of such homogeneous 1:2 cobalt complexes.

The sulpho group is preferably bound to the B or R₁ nucleus, more preferably to the R₁ nucleus.

Where R₁ is alkyl, preferably such alkyl is methyl or ethyl. When R₁ is ##STR9## then R₂ is preferably R₂ ', where R₂ ' is hydrogen or chlorine, especially hydrogen; R₃ is preferably R₃ ', where R₃ ' is hydrogen or --SO₃ H, more preferably R₃ ", where R₃ " is --SO₃ H in the 3- or 4- position.

Preferably, R₁ is R₁ ', where R₁ ' is hydrogen or ##STR10## in which R₃ ' is as defined above; more preferably, R₁ is R₁ ", where R₁ " is ##STR11## where R₃ " is as defined above.

Preferably, B is a group of formula (b) as given above. More preferably B is a group of formula (b) in which m is 1.

Any alkyl or alkoxy radicals as significances for R₄ and/or R₅ are preferably methyl or methoxy radicals.

Preferably, R₄ is R₄ ', where R₄ ' is hydrogen, chlorine or nitro. More preferably, R₄ is R₄ ", where R₄ " is chlorine or nitro.

Preferably, R₅ is R₅ ', where R₅ ' is hydrogen, chlorine, nitro or --SO₃ H. More preferably, R₅ is R₅ ", where R₅ " is hydrogen, chlorine or nitro, with nitro being especially preferred.

When both R₄ and R₅ have a significance other than hydrogen, they are preferably in the 4,6-positions.

Where one of R₆ and R₇ is --SO₂ NR₈ R₉, any alkyl group as R₈ and R₉ is straight-chain or branched and is unsubstituted or monosubstituted by halogen, such as chlorine or bromine, hydroxy, cyano, phenyl or (C₁₋₄), preferably (C₁₋₂), alkoxy. Preferred substituents are hydroxy, methoxy and ethoxy, with hydroxy being especially preferred. Where one of R₈ and R₉ is unsubstituted alkyl, preferably such alkyl is (C₁₋₃), more preferably methyl, ethyl or isopropyl.

Where R₉ is unsubstituted or substituted cycloalkyl, such cycloalkyl preferably contains 5 or 6 carbon atoms, with cyclohexyl groups being especially preferred. Substituted cycloalkyl groups as R₉ are preferably mono-, di- or trimethyl-substituted cycloalkyls.

Where R₉ signifies phenyl, such phenyl is preferably unsubstituted. Where R₉ is substituted phenyl the phenyl ring is preferably substituted by up to 3 substituents selected from halogen, such as fluorine, chlorine and bromine, nitro, (C₁₋₄)alkyl and (C₁₋₄)alkoxy. Preferred substituents are chlorine, nitro, methyl, methoxy and ethoxy. Preferably, when substituted the ring is monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy.

Where R₈ and R₉, together with the nitrogen atom, form a heterocyclic ring, preferably they form a pyrrolidine, piperidine or morpholine ring.

Preferably, R₈ is R₈ ', where R₈ ' is hydrogen, (C₁₋₃)alkyl or (C₂₋₃)hydroxyalkyl. More preferably R₈ is hydrogen.

Preferably, R₉ is R₉ ', where R₉ ' is hydrogen, (C₁₋₃)alkyl, (C₂₋₃)hydroxyalkyl, methoxy- or ethoxy-(C₂₋₄), preferably (C₂₋₃), alkyl, unsubstituted phenyl, phenyl monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy or phenyl substituted by two methyl, methoxy or ethoxy groups. More preferably R₉ is R₉ ", where R₉ " is hydrogen, methyl, ethyl, isopropyl, β-hydroxyethyl, 2-hydroxy-n-propyl, --(CH₂)₃ --OCH₃ or unsubstituted phenyl. Even more preferably, R₉ is R₉ '", where R₉ '" is hydrogen, methyl, --(CH₂)₃ --OCH₃ or unsubstituted phenyl, with hydrogen and --(CH₂)₃ --OCH₃ being especially preferred.

Preferably, one of R₆ and R₇ is --SO₂ NHR₉ ', more preferably --SO₂ NHR₉ ", most preferably --SO₂ NHR₉ '" and the other is hydrogen. The complexes where R₆ is --SO₂ NH₂ or --SO₂ NH(CH₂)₃ OCH₃ and R₇ is hydrogen are especially preferred.

When one of R₁₀ and R₁₁ is alkoxy, such alkoxy is preferably methoxy.

Preferably, R₁₀ is R₁₀ ', where R₁₀ ' is hydrogen, chlorine, methyl, ethyl or methoxy and R₁₁ is hydrogen. More preferably both R₁₀ and R₁₁ are hydrogen.

R₁₃ is preferably methyl.

Any alkyl group for R₁₄ and R₁₅ may be straight chain or branched. The preferred unsubstituted alkyls are methyl and ethyl. Any substituted alkyl as R₁₄ and R₁₅ is preferably substituted by the substituents given above for the substituted alkyl radicals as R₈ and R₉. Any substituted phenyl is preferably substituted by the substituents given above for substituted phenyl radicals as R₉. Preferably, any phenyl radical as R₁₄ and R₁₅ is unsubstituted.

Preferably, R₁₄ and R₁₄ ', where R₁₄ ' is methyl, ethyl or phenyl and R₁₅ is R₁₅ ', where R₁₅ ' has one of the significances of R₁₄ '.

Any alkyl as Z preferably contains 1 or 2 carbon atoms, with methyl being especially preferred. Any substituted phenyl as Z preferably bears the substituents given above for substituted phenyl as R₉. When Z is --NR₁₆ R₁₇, preferably each of R₁₆ and R₁₇ is methyl.

Preferably, Z is Z₁, where Z₁ is alkyl or --NR₁₆ R₁₇, with --N(CH₃)₂ being especially preferred. Preferably, Y₁ is Y₁ ', where Y₁ ', is hydrogen, --NHCOR₁₄ ', --NHCOOR₁₅ ' or --NHSO₂ Z₁, where R₁₄ ', R₁₅ ' and Z₁ are as defined above. More preferably Y₁ " is hydrogen, --NHCOR₁₄ ' or --NHSO₂ --N(CH₃)₂, with hydrogen being especially preferred.

Y₂ is preferably Y₂ ' where Y₂ ' is methyl or methoxy. Where R₁₈ is alkyl, such alkyl preferably contains 1 or 2 carbon atoms, with methyl being especially preferred. When R₁₈ is hydroxyalkyl such hydroxyalkyl preferably contains 2 or 3 carbon atoms and is preferably a β-hydroxyalkyl.

Preferably, R₁₈ is R₁₈ ', where R₁₈ ' is hydrogen, methyl or β-hydroxy(C₂₋₃)alkyl.

When Y₃ is --SO₂ NHR₁₈ in the 5- or 6-position such --SO₂ NHR₁₈ is preferably --SO₂ NHR₁₈ ' where R₁₈ ' is as defined above and is preferably in the 6-position.

One set of complexes of formula I are those where --X--D-- is a radical of formula (c); another set where --X--D-- is a radical of formula (d); another set where --X--D-- is a radical of formula (e); another set where --X--D-- is a radical of formula (f); another set where --X--D-- is a radical of formula (g); and another set where --X--D-- is a radical of formula (h).

The group --X--D-- is preferably a radical of formula (c), (d), (e), (f) or (h) as defined above; more preferably it is a group of formula (c) or (f).

As examples of non-chromophoric cations as M⊕ can be given, alkali metal cations, such as lithium, sodium or potassium, sodium being the preferred alkali metal cation; N⊕R₄ wherein each R is, independently, hydrogen, (C₁₋₃)alkyl or hydroxy(C₂₋₃)alkyl with the proviso that when one or more of the symbols R signifies hydroxyalkyl at least one R signifies hydrogen. Examples of such alkylammonium ions are mono-, di-, tri- and tetra-methylammonium, triethylammonium and mono-, di- and tri-ethylammonium.

However, quaternized amines which reduce the water-solubility of the 1:2 cobalt complexes so that they are only soluble in the presence of organic solvents are also suitable cations. Examples of suitable amines are N-ethyl-N-hexylamine, cyclohexylamine, N,N-dicyclohexylamine and cyclic amines such as morpholine.

The salt form of the --SO₃ H group may correspond to any of the above mentioned cations for M⊕. The salt form cation may be the same as or different from M⊕. Among the preferred homogeneous 1:2 cobalt complexes of formula I and mixtures of complexes are those wherein R₁ is R₁ ', R₄ is R₄ ', R₅ is R₅ ', one of R₆ and R₇ is -SO₂ NHR₉ ' and the other is hydrogen, each of R₁₄ and R₁₅ is C₁₋₄ alkyl; C₁₋₄ alkyl monosubstituted by halo, hydroxy, cyano, phenyl or C₁₋₄ alkoxy; phenyl or phenyl monosubstituted by chloro, nitro, methyl, methoxy or ethoxy or disubstituted by methyl, methoxy or ethoxy and B is a radical of formula (b).

Preferred complexes of formula I are those of formula Ia, ##STR12## in which R₁ ', R₄ ", R₅ ", m, R₉ " and M⊕ are as defined above, and

--X'-- is --O-- or ##STR13## in which R₁₀ ' is as defined above and R₁₁ ' is hydrogen, the sulpho group being in the 5-or 6-position when m is 2.

Even more preferred compounds of formula I are those of formula Ib, ##STR14## in which R₄ ", R₅ ", R₉ "' and M.sup.⊕ are as defined above,

--X--" is --O-- or ##STR15## and the sulpho group is in the 3- or 4-position.

Especially preferred are the complexes of formula Ib in which R₄ " is nitro, more preferably both R₄ " and R₅ " are nitro.

The preferred mixtures of the 1:2 complexes of formula I are mixtures of at least one compound of formula I in which the group --X--D-- is a group of formula (f), (g) or (h) with a compound of formula I in which --X--D-- is a group of formula (c), (d) or (e). Preferably 30 to 70% of the compound or compounds having a group --X--D-- of formula (f), (g) or (h) is employed; more preferably, the mixtures are 1:1 mixtures.

The invention also provides a process for the production of homogeneous asymmetric complexes of formula I, or mixtures of such asymmetric complexes, comprising

(a) reacting a 1:1 complex of formula II or a mixture thereof, ##STR16## in which L₁ and L₂ are both monodentate ligands, and R₁, R₄, R₅ and B are as defined above,

with a compound of formula III, or a mixture thereof, ##STR17## in which R₆, R₇ and --X--D-- are as defined above, or (b) reacting a corresponding nitrite containing cobalt complex of the compound of formula III or a mixture thereof, where --D--X-- is a group of formula (f), (g) or (h) with a compound of formula IV, ##STR18## in which R₁, R₄, R₅ and B are as defined above, or a mixture thereof.

Preferably, the reactants are employed in stoichiometric amounts. The ligands L₁ and L₂ may, for example, be colourless inorganic or organic molecules which have an oxygen-containing or nitrogen-containing group with electron donating properties, in particular water molecules. The reaction is conveniently conducted in aqueous and/or organic solvent medium. As examples of suitable organic solvents may be given aliphatic carboxylic acid amides, such as formamide or an alkylated derivative thereof; glycols such as ethyleneglycol, di- or tri-ethyleneglycol or ether derivatives thereof. The reaction is suitably conducted in a neutral or alkaline medium and is completed after all the 1:1 cobalt complex has been reacted. The 1:2 cobalt complex obtained may be salted out in conventional manner an after washing in a concentrated salt solution may be collected and dried. When mixtures of starting materials are used, the reaction is conducted in similar manner.

The obtained 1:2 cobalt complexes are homogeneous asymmetric complexes. By homogeneous is meant that the obtained asymmetric 1:2 complexes contain less than 10% by the possible symmetric complexes.

The starting material of formula II may, for example, be prepared by reacting a compound of formula IV, as defined above, with a cobalt-donating compound, preferably employing, at least one mole of the cobalt-donating compound per mole of the compound of formula IV. The cobalt-donating compound is suitably a cobalt (II) salt. The reaction is suitably conducted in the presence of an inorganic nitrite, preferably in a ratio of 2 to 6 moles of the nitrite per gram atom of cobalt. The metallization may be conducted in conventional manner.

Depending on the reaction and isolation conditions (e.g. addition of base to obtain an alkaline pH or the salt used to salt-out the product) a complex of formula I is obtained in which M.sup.⊕ is preferably an alkali metal cation such as lithium, sodium or potassium or an ammonium ion and in which the cation M.sup.⊕ is the same or different as the cation of the sulpho group in the salt form. When a weak acid is used, a complex is obtained in which M.sup.⊕ is hydrogen. The hydrogen ion may be replaced by an alkali metal cation or quaternary ammonium ion by the addition of alkali metal hydroxides or organic amines. Preferably, M.sup.⊕ is other than hydrogen.

The complexes of formula I and their mixtures are useful for dyeing and printing nitrogen-containing organic substrates. Examples of suitable substrates are those which consist of or comprise natural and synthetic polyamides such as wool, silk or nylon, polyurethane fibres and leather. Dyeings with reddish- to greenish-grey shades are, in most cases, obtained. By employing mixtures of the complexes of formula I dyeings with neutral grey shades may be obtained.

The dyeings obtained exhibit notable light- and wet-fastness properties. Furthermore, they are fast to rubbing and show notable resistance to carbonization, ironing, wool chlorination and the action of acids and alkalis. They build-up from a neutral dyeing medium on polyamide fibres, the build-up being tone-in-tone due to their homogeneous asymmetric character. In printing pastes they build-up well on all types of polyamides.

The complexes of formula I which are well-soluble in water, i.e. those which have cations other than the aforementioned quaternary amines such as N-ethyl-N-hexylamine, cyclohexylamine, N,N-dicyclohexylamine or cyclic amines in quaternary form, are useful for dyeing metals, especially anodized aluminum .

The complexes of formula I which are soluble in organic solvents and are scarcely or totally insoluble in water, i.e. those having quaternary amine cations as referred to above, may be used in the preparation of printing lacquers and bal-point pen inks.

The following Examples further serve to illustrate the invention. In the Examples the parts are by weight and the temperatures are in degrees Centigrade.

EXAMPLE 1

The 1:1 cobalt complex obtained from 51 parts of the monoazo dyestuff 2-amino-1-hydroxy-4,6-dinitrobenzene → 2phenylaminonaphthalene-4'-sulphonic acid is stirred into 800 parts of water at 50° together with 34 parts of the dyestuff obtained by coupling diazotised 2-amino-1-hydroxybenzene-4-sulphonic acid amide with 2-hydroxynaphthalene. The pH is adjusted to 12 by the addition of caustic soda and stirring is continued for some hours at 40°-50° until the 1:1 cobalt complex has completely disappeared. The chromatograph of the asymmetric 1:2 cobalt complex thus obtained should no longer show metal-free dyestuff or only slight traces thereof. The dyestuff solution is filtered and the product is salted out by the addition of sodium chloride. Finally, the dyestuff is filtered, washed with a 10% sodium chloride solution and dried; it corresponds to the formula ##STR19##

The dyestuff is well soluble in water and dyes natural and synthetic polyamide fibres such as wool and nylon is reddish-grey shades. The dyeing has good all-round wet fastness and fastness to rubbing and light.

The 1:1 cobalt complex used as the initial material may be produced as follows:

28 parts of cobalt-(II)-sulphate.7H₂ O and 21 parts of sodium nitrite and dissolved in a beaker containing 500 parts of water and 100 parts of dimethyl formamide, then 51 parts of the monoazo dyestuff 2-amino-4,6-dinitro-1-hydroxybenzene → 2-phenylaminonaphthalene-4'-sulphonic acid are added with stirring. During and after the addition of the monoazo dyestuff the pH is set at 5.0 - 5.5 with dilute hydrochloric acid and it is kept in this range for about 24 hours, until the initial dyestuff has been completely converted into the 1:1 cobalt complex. During metallization, the temperature is maintained at 20°to 30°. The 1:1 cobalt complex is precipitated by salting out, filtered off and washed with a 5% sodium chloride solution until the filtrate is free of cobalt. The 1:1 cobalt complex may be used as such to form the assymetrical 1:2 cobalt complex.

EXAMPLE 2

The 1:1 cobalt complex produced as described in Example 1, 21 parts of the dyestuff obtained by acid coupling of diazotised 2-amino-1-hydroxybenzene-4-sulphonic acid amide with 2-phenylaminonaphthalene and 17 parts of the dyestuff obtained by alkaline coupling of diazotised 2-amino-1-hydroxybenzene-4-sulphonic acid amide with 2-hydroxynaphthalene are stirred into 800 parts of water at 20° . Subsequently, 250 parts of a 30% sodium hydroxide solution are added and stirring continued at 20° until the 1:1 cobalt complex has been completely converted into 2 asymmetrical 1:2 cobalt complexes, at which the two unmetallized dyestuffs should no longer be detectable, or only in slight traces. The mixture of the two asymmetrical complexes is precipitated by adding sodium chloride, it is filtered off, washed with 10% sodium chloride solution and dried.

The dried dyestuff is well soluble in water and dyes natural and synthetic polyamide fibres such as wool and nylon in grey shades. The dyeings have good fastness to light and good all-round wet fastness. Furthermore, the dyeings are resistant to acid and alkali and are fast to rubbing. Leather dyeings obtained with the above mixture have good light fastness.

Further dyestuff complexes are given in the following Table and have the structure indicated; they may be produced in analogy with the procedure described in Example 1 and are in sodium salt form. On polyamides they yield dyeings which have similar properties to those obtained with the dyestuffs of Examples 1 and 2, such dyeings have the following shades:

grey: Examples 5, 7, 8, 10, 13 to 15, 17 to 26, 28 to 33, 35, 39, 41, 42, 49 and 50

reddish-grey: Examples 6 and 27

bluish-grey: Examples 34, 46 to 48 and 51

olive-gray: Example 45

greenish-grey: Examples 3, 4, 11, 12, 36 to 38, 40, 43 and 44

green: Example 9

dark brown: Example 16

    __________________________________________________________________________     Example                                                                        No.  Compound of formula IV                                                                               Compound(s) of formula III                          __________________________________________________________________________     3    2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-4-                              benzene → 2-phenylamino-                                                                      sulphonic acid amide → 2-                         naphthalene-4'-sulphonic acid                                                                        phenylaminonaphthalene                              4        "                 2-amino-1-hydroxybenzene-4-                                                    sulphonic acid amide → 2-                                               (3'-chlorophenylamino)naph- -   thalene             5        "                 2-amino-1-hydroxybenzene-4-                                                    sulphonic acid amide → 2-                                               phenylaminonaphthalene +                                                       2-amino-1-hydroxybenzene-4-                                                    sulfonic acid N-3'-methoxy-                                                    propylamide → 2-hydroxynaph-                                            thalene                                             6        "                 2-amino-1-hydroxybenzene-4-N-                                                  (3'-methoxypropyl)sulphonic                                                    acid amide → 2-hydroxynaph-                                             thalene                                             7        "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 8-                                                  acetylamino-2-hydroxynaphthalene                    8        "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 8-(N,N-                                             dimethylsulphamoyl)amino-2-                                                    hydroxynaphthalene                                  9    2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-4-                              benzene → 2-aminonaph-                                                                        sulphonic acid amide → 2-                         thalene-6-sulphonic acid                                                                             aminonaphthalene                                    10   2-amino-1-hydroxy-4-nitro-                                                                               "                                                    benzene-6-sulphonic acid →                                              2-phenylaminonaphthalene                                                  11       "                 2-amino-1-hydroxybenzene-4-N-                                                  phenylsulphonic acid amide →                                            2-phenylaminonaphthalene                            12       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 2-                                                  phenylaminonaphthalene                              13   2-amino-1-hydroxybenzene-4-                                                                              "                                                    sulphonic acid → 2-                                                     phenylaminonaphthalene                                                    14   2-amino-1-hydroxybenzene →                                                                    2-amino-1-hydroxybenzene-4-sul-                          2-aminonaphthalene-6-sulphon-                                                                        phonic acid amide → 2-                            ic acid               phenylaminonaphthalene                              15   2-amino-1-hydroxy-4-nitro-                                                                           2-amino-1-hydroxybenzene-4-sul-                          benzene → 2-aminonaph-                                                                        phonic acid amide → 2-                            thalene-6-sulphonic acid                                                                             phenylaminonaphthalene                              16       "                 2-amino-1-hydroxybenzene-4-                                                    sulfonic acid N-3'-methoxy-                                                    propylamide → 2-hydroxynaphthalene           17       "                 2-amino-1-hydroxybenzene-4-N-                                                  phenylsulphonic acid amide →                                            2-phenylaminonaphthalene                            18   2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-4-sul-                          benzene → 2-aminonaphtha-                                                                     phonic acid amide → 2-phenyl-                     lene-6-sulphonic acid aminonaphthalene +                                                             2-amino-1-hydroxybenzene-4-                                                    sulfonic acid N-3'-methoxy-                                                    propylamide → 2-hydroxynaphthalene           19   2-amino-1-hydroxy-4,6-dinitro-                                                                           "                                                    benzene → 1-aminonaphtha-                                               lene-4-sulphonic acid                                                     20   2-amino-1-hydroxy-4-nitro-                                                                           2-amino-1-hydroxybenzene-4-sul-                          benzene → 1-aminonaphtha-                                                                     phonic acid amide → 2-phenyl-                     lene-4-sulphonic acid aminonaphthalene                                    21   2-amino-1-hydroxy-4-nitro-                                                                               "                                                    benzene → 1-amino-                                                        2nd position                                                                 naphthalene-5-sulphonic acid                                              22   2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-5-sul-                          benzene → 2-phenylaminonaph-                                                                  phonic acid amide → 2-hydroxy-                    thalene-4'-sulphonic acid                                                                            naphthalene                                         23       "                 2-amino-1-hydroxybenzene-5-N-                                                  sulfonic acid methylamide →                                             2-hydroxynaphthalene                                24       "                 2-amino-4-chloro-1-hydroxybenzene                                              5-sulphonic acid amide → 2-                                             hydroxynaphthalene                                  25   2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxy-5-nitrobenzene-                        benzene → 2-phenylaminonaph-                                                                  4-sulphonic acid amide → 2-                       thalene-4'-sulphonic acid                                                                            hydroxynaphthalene                                  26       "                 2-amino-1-hydroxybenzene-5-                                                    sulfonic acid-N-methylamide →                                           1-hydroxy-5,8-dichloronaphthalene                   27       "                 2-amino-1-hydroxybenzene-4-                                                    sulfonic acid N-isopropylamide                                                 → 2-(2',6'-dimethylphenyl-                                              amino)naphthalene                                   28       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 1-hydroxy-                                          4-methylnaphthalene                                 29       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 1-hydroxy-                                          4-methoxynaphthalene                                30       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 1-hydroxy-                                          5,8-dichloronaphthalene                             31   2-amino-1-hydroxy-4-nitro-                                                                               "                                                    benzene → 2-aminonaphtha-                                               lene-6-sulphonic acid                                                     32       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 1-hydroxy-                                          4-methylnaphthalene                                 33       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 1-hydroxy-                                          4-methoxynaphthalene                                34   2-amino-4-chloro-1-hydroxy-                                                                          2-amino-1-hydroxybenzene →                        benzene-6-sulphonic acid                                                                             2-amino-naphthalene-6-                                   → 2-aminonaphthalene                                                                          sulfonic acid N-2'-hydroxy-                                                    propylamide                                         35   2-amino-1-hydroxy-6-methyl-                                                                          2-amino-1-hydroxybenzene-4-sul-                          4-nitrobenzene → 2-                                                                           phonic acid amide → 8-benzoyl-                    aminonaphthalene-5-sulphonic acid                                                                    amino-2-hydroxynaphthalene                          36   2-amino-1-hydroxy-4-methyl-6-                                                                        2-amino-1-hydroxybenzene-4-                              nitrobenzene → 2-aminonaph-                                                                   sulfonic acid N,N-dimethylamide →                 thalene-6-sulphonic acid                                                                             2-(4'-methoxyphenylamino)naph-                                                 thalene                                             37   2-amino-1-hydroxy-4-methoxy-                                                                         2-amino-1-hydroxybenzene-4-                              benzene → 1-amino-                                                                            sulfonic acid N-2' methoxyethyl-                           2nd position        amide → 2-phenylaminonaph-                        naphthalene-5-sulphonic acid                                                                         thalene                                             38   2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-4-sul-                          benzene → 1-aminonaphtha-                                                                     phonic acid amide → 2-(4'-                        lene-4-sulphonic acid chlorophenyl-amino)naphthalene                      39   2-amino-1-hydroxy-4,6-dinitro-                                                                       2-amino-1-hydroxybenzene-5-sul-                          benzene → 2-(3'-chloro-                                                                       phonic acid morpholine → 2-                       phenylamino)naphthalene-4'-                                                                          hydroxynaphthalene                                       sulphonic acid                                                            40   2-amino-1-hydroxy-4-methyl-                                                                          2-amino-1-hydroxy-4-nitrobenzene                         benzene-6-sulphonic acid →                                                                    → 2-aminonaphthalene-6-                           2-(4'-methylphenylamino)naph-                                                                        sulfonic acid N-methylamide                              thalene                                                                   41   2-amino-1-hydroxy-6-nitro-4-                                                                         2-amino-1-hydroxybenzene-4-sul-                          propylbenzene → 2-amino-                                                                      phonic acid amide → 8-ethoxy-                     naphthalene-6-sulphonic acid                                                                         carbonylamino-2-hydroxynaphthalene                  42   2-amino-4,6-dichloro-1-hydroxy-                                                                      2-amino-1-hydroxybenzene-4-                              benzene → 2-aminonaphtha-                                                                     sulfonic acid N,N-diethylamide →                  lene-6-sulphonic acid 8-acetylamino-2-hydroxynaphthalene                  43   2-amino-4-chloro-1-hydroxy-                                                                          2-amino-1-hydroxybenzene-4-                              6-nitrobenzene → 2-                                                                           sulfonic acid N-2'-hydroxyethylamide                     aminonaphthalene-5-sulphonic acid                                                                    → 2-phenylaminonaphthalene                   44   2-amino-6-chloro-1-hydroxy-4-                                                                        2-amino-1-hydroxybenzene-4-                              nitrobenzene → 2-aminonaph-                                                                   sulfonic acid N-2'-hydroxypropyl-                        thalene-5-sulphonic acid                                                                             amide → 2-phenylaminonaph-                                              thalene                                             45   2-amino-1-hydroxy-6-nitro-                                                                           2-amino-1-hydroxybenzene-5-                              benzene-4-sulphonic acid →                                                                    sulfonic acid N-methylamide →                     2-ethylaminonaphthalene                                                                              2-(2'-methylphenylamino)naphtha-                                               lene                                                46   2-amino-1-hydroxy-5-nitro-                                                                           2-amino-1-hydroxybenzene-4-sul-                          benzene →  2-aminonaphtha-                                                                    phonic acid morpholine → 2-                       lene-6-sulphonic acid (4'-ethylphenylamino)naphthalene                    47   2-amino-1-hydroxy-4,6-dini-                                                                          2-amino-1-hydroxybenzene-4-sul-                          trobenzene → 2-aminonaph-                                                                     phonic acid amide → 2-phenyl-                     thalene-5-sulphonic acid                                                                             aminonaphthalene                                    48       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 8-acetyl-                                           amino-2-hydroxynaphthalene                          49   2-amino-1-hydroxy-4-nitro-                                                                           2-amino-1-hydroxybenzene-4-sul-                          benzene → 2-aminonaph-                                                                        phonic acid amide → 8-acetyl-                     thalene-5-sulphonic acid                                                                             amino-2-hydroxynaphthalene                          50       "                 2-amino-1-hydroxybenzene-4-sul-                                                phonic acid amide → 2-                                                  phenylaminonaphthalene                              51   2-amino-1-hydroxy-4,6-dini-                                                                              "                                                    trobenzene → 1-amino-                                                     2nd position                                                                 naphthalene-5-sulphonic acid                                              52   2-amino-1-hydroxy-4-nitrobenzene                                                                   "                                                          → 2-phenylaminonaphthalene-6-sulfonic                                   acid                                                                      __________________________________________________________________________

APPLICATION EXAMPLE A

0.05 g of the dyestuff obtained in accordance with Example 1 is dissolved in 300 parts of water, 0.2 g o ammonium sulphate being added thereto. Subsequently, the steeped material (5 g of wool gaberdine or 5 g of nylon-satin) is entered into the bath which is heated over the course of 30 minutes to boiling temperature. The water which evaporated is replaced and dyeing is completed at boiling temperature for a further 30 minutes. The material is then rinsed. After drying, a reddish-grey dyeing is obtained which has good light and wet fastness.

The dyestuffs of Examples 2 to 51 may be employed in analogous manner.

APPLICATION EXAMPLE B

Polyamides are printed with a printing paste of the following formulation:

30 parts of the dyestuff of Example 3,

50 parts urea,

50 parts dissolving agent for example, thiodiethyleneglycol

300 parts water,

500 parts suitable thickening agent for example, based on a locust bean gum,

60 parts acid acceptor for example, ammonium tartrate, and

60 parts thiourea.

The printed textile goods are steamed for 40 minutes at 102° (saturated steam), then rinsed with cold water, washed for 5 minutes at 60° with a dilute solution of a conventional detergent and then rinsed again. A bluish-olive printe with good wet and light fastnesses is obtained.

The dyestuffs of Examples 1, 2 and 4 to 51 may be used in analogous manner to print polyamides. 

What is claimed is:
 1. A homogenous complex of the formula ##STR20## or a mixture of such complexes, wherein R'₁ is hydrogen or ##STR21## wherein R'₃ is hydrogen or --SO₃ M, R'₄ is hydrogen, chloro or nitro,R'₅ is hydrogen, chloro, nitro or --SO₃ M,with the proviso that when only one of R'₄ and R'₅ is hydrogen, the one that is other than hydrogen is in the 4- or 5-position, and when both R'₄ and R'₅ are other than hydrogen, they are in the 4,5- or 4,6-positions, one of R'₆ and R'₇ is --SO₂ NHR'₉ and the other is hydrogen,wherein R'₉ is hydrogen; C₁₋₃ alkyl; C₂₋₃ hydroxyalkyl; methoxy(C₂₋₄ alkyl); ethoxy(C₂₋₄ alkyl); phenyl; phenyl monosubstituted by chloro, nitro, methyl, methoxy or ethoxy or phenyl disubstituted by methyl, methoxy or ethoxy, ##STR22## wherein one of R₁₀ and R₁₁ is hydrogen, chloro, C₁₋₂ alkyl, C₁₋₂ alkoxy or trifluoromethyl and the other is hydrogen,R₁₂ is hydrogen or methyl, R₁₃ is methyl, chloro or bromo, with the proviso that when R₁₃ is chloro or bromo, R₁₂ is hydrogen, Y₁ is hydrogen, --NHCOR₁₄, --NHCOOR₁₅ or --NHSO₂ NR₁₆ R₁₇,wherein each of R₁₄ and R₁₅ is C₁₋₄ alkyl; C₁₋₄ alkyl mono-substituted by halo, hydroxy, cyano, phenyl or C₁₋₄ alkoxy; phenyl; phenyl monosubstituted by chloro, nitro, methyl, methoxy or ethoxy or phenyl disubstituted by methyl, methoxy or ethoxy, R₁₆ is hydrogen, methyl or ethyl, and R₁₇ is methyl or ethyl, and Y₂ is hydrogen, C₁₋₂ alkyl, C₁₋₂ alkoxy, chloro or bromo, wherein the asterisk indicates the carbon atom attached to the --N═N-- radical, M' is 0 or 1,with the proviso that when m' is 1 the --SO₃ M group is in the 5- or 6-position, M.sup.⊕ is hydrogen or a non-chromophoric cation, and M is a non-chromophoric cation,with the provisos that (i) the complex contains a single --SO₃ M group, and (ii) the complex is free of ##STR23##
 2. A homogeneous complex according to claim 1, or a mixture of such complexes,wherein M.sup.⊕ is hydrogen, lithium, sodium, potassium or .sup.⊕ NR₄,wherein each R is independently hydrogen, C₁₋₃ alkyl or C₂₋₃ hyroxyalkyl, with the proviso that at least one R is hydrogen when any R is C₂₋₃ hydroxyalkyl, and M is lithium, sodium, potassium or .sup.⊕ NR₄,wherein each R is independently hydrogen, C₁₋₃ -alkyl or C₂₋₃ hydroxyalkyl, with the proviso that at least one R is hydrogen when any R is C₂₋₃ -hydroxyalkyl.
 3. A homogeneous complex according to claim
 2. 4. A homogeneous complex according to claim 2, or a mixture of such complexes,wherein M.sup.⊕ is sodium, and M is sodium.
 5. A homogeneous complex according to claim 1 having the formula ##STR24## or a mixture of such complexes, wherein R'₁ is hydrogen or ##STR25## wherein R'₃ is hydrogen or --SO₃ M, R"₄ is chloro or nitro,R"₅ is hydrogen, chloro or nitro,with the proviso that when R"₅ is hydrogen, R"₄ is in the 4- or 5-position, and when R"₅ is chloro or nitro, R"₄ and R"₅ are in the 4,5- or 4,6-positions, R"₉ is hydrogen, methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-hydroxy-n-propyl, 3-methoxypropyl or phenyl, --X'-- is --O-- or ##STR26## wherein R'₁₀ is hydrogen, chloro, methyl, ethyl or methoxy, M.sup.⊕ is hydrogen or a non-chromophoric cation, M is a non-chromophoric cation, and m' is 0 or 1,with the proviso that m' is 0 when R'₁ is ##STR27## and is otherwise 1, with the proviso that the complex is free of ##STR28##
 6. A homogeneous complex according to claim 5 having the formula ##STR29## or a mixture of such complexes, wherein R"₄ is chloro or nitro,R"₅ is hydrogen, chloro or nitro, R"₉ is hydrogen, methyl, 3-methoxypropyl or phenyl, --X"-- is --O-- or ##STR30## M.sup.⊕ is hydrogen or a non-chromophoric cation, and M is a non-chromophoric cation,with the proviso that the --SO₃ M group is in the 3- or 4-position.
 7. A homogeneous complex according to claim 6, or a mixture of such complexes,wherein R"₄ is nitro, and R"₅ is nitro.
 8. a homogeneous complex according to claim 7 having the formula ##STR31## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 9. The homogeneous complex according to claim 8wherein M.sup.⊕ is sodium, and M₁ is sodium.
 10. A homogeneous complex according to claim 7 having the formula ##STR32## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 11. The homogeneous complex according to claim 10wherein M.sup.⊕ is sodium, and M₁ is sodium.
 12. A mixture of homogeneous complexes according to claim 7 having the formulae ##STR33## wherein M.sup.⊕ is hydrogen or a non-chromophoroic cation, and M₁ is a non-chromophoric cation.
 13. A mixture of homogeneous complexes according to claim 7 having the formulae ##STR34## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 14. A homogeneous complex according to claim 1 having the formula ##STR35## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 15. The homogeneous complex according to claim 14wherein M.sup.⊕ is sodium, and M₁ is sodium.
 16. A homogeneous complex according to claim 1 having the formula ##STR36## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 17. The homogeneous complex according to claim 16wherein M.sup.⊕ is sodium, and M₁ is sodium.
 18. A homogeneous complex according to claim 1 having the formula ##STR37## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 19. A homogeneous complex according to claim 1 having the formula ##STR38## wherein M.sup.⊕ is hydrogen or a non-chromophoric cation, and M₁ is a non-chromophoric cation.
 20. The homogeneous complex according to claim 19wherein M.sup.⊕ is sodium, and M₁ is sodium.
 21. The homogeneous complex according to claim 1 having the formula ##STR39##
 22. The homogeneous complex according to claim 1 having the formula ##STR40##
 23. The homogeneous complex according to claim 1 having the formula ##STR41##
 24. The homogeneous complex according to claim 1 having the formula ##STR42## 